Gentle oxidation hair color with medium oxidan composition

ABSTRACT

The subject matter of the present invention is an oxidative coloring agent for oxidatively changing the color of keratinic fibers, in particular human hair, which is produced immediately before utilization by mixing at least one composition (A) containing, in a cosmetically suitable carrier, at least one alkalizing agent, at least one oxidation dye precursor of the developer type, and at least one oxidation dye precursor of the coupler type, with at least one composition (B) containing, in a cosmetically suitable carrier, at least one cosmetic oil in a total quantity from 10 to 80 wt % based on the weight of composition (B), and hydrogen peroxide, wherein at least one of the compositions (A) or (B) contains at least one 4-morpholinomethyl-substituted silicone of formula (V).

CROSS REFERENCE TO RELATED APPLICATION

This application claims priority to German Patent Application No. DE 102012 223 803.4, filed Dec. 19, 2012, its contents hereby incorporated inits entirety.

TECHNICAL FIELD

The present invention relates to a hair-protecting coloring agent foroxidative hair coloring, and to a low-impact method for oxidative haircoloring in which keratinic fibers are protected from oxidizinginfluences.

BACKGROUND

In oxidative hair coloring, the problem arises that irritation of thescalp and damage to the keratinic fibers can occur as a result of theaggressive agents. In particular, the natural hydrophobicity of thekeratinic fibers is reduced because the coloring agents resp. lighteningagents must first make the hair capable of penetration in order to exerttheir effect. The water-repellent effect on the one hand, however,provides natural protection for the hair; on the other hand, parametersdesired by the consumer, such as shine, softness, suppleness, and the“drape” of the hair, are closely linked to it.

In order to overcome the aforesaid disadvantages, so-called pretreatmentagents that are intended to protect the hair from aggressive influencesare on the market. These often make the hair heavy, however, ornegatively affect the outcome of the lightening resp. coloring of thehair that takes place subsequently; in particular, the washing fastnessof the color can be degraded by the pretreatment agent. Also known arenumerous post-treatment agents with which an attempt is made to repairthe hair damage caused in the context of the oxidative coloringtreatment. All these methods, however, require a multi-step utilizationmethod, and even application of a further hair treatment agent eitherbefore or after coloring. This is often perceived by the consumer asburdensome, since the oxidative coloring treatment itself, with multipleworking steps and a contact time of up to 60 minutes, is already verylaborious.

SUMMARY

An object of the present invention is to make available an agent and amethod for oxidative hair coloring, with a hair-protecting treatment,that overcomes the aforesaid disadvantages without negativelyinfluencing the color result of the oxidative coloring treatment. Theintention is in particular to make available a coloring agent and amethod in which the hair is not made heavier, and the least possiblehair damage occurs. The hair protection achieved is furthermore intendedto consume as little time as possible, and if possible to take placetogether with the coloring step.

DETAILED DESCRIPTION

The use of aminated silicones in hair care is established art. They arewidely used in shampoos and in particular in conditioners in order toexert care-providing effects therein. EP 1771144 B1, for example,discloses hair-conditioning agents having aminofunctional silicones. Theagents described therein are post-treatment agents.

European patents EP 1312334 B1 (aminosilicone and thickener) and EP1312335 B1 (aminosilicone and conditioner) also disclose hairpost-treatment agents.

It has now been found that a coloring agent containing special4-morpholinomethyl-substituted silicones results in appreciably improvedhair protection in the context of oxidative coloring treatment, with nonegative effect on the results of the oxidative coloring treatment. Inaddition, particularly good coloring results, in particular colorshaving a high level of washing fastness, are achieved with the coloringagents according to the present invention.

The subject matter of the present invention is, in a first embodiment,an oxidative coloring agent for oxidatively changing the color ofkeratinic fibers, in particular human hair, which is producedimmediately before utilization by mixing at least one composition (A)containing, in a cosmetically suitable carrier, at least one alkalizingagent, at least one oxidation dye precursor of the developer type, andat least one oxidation dye precursor of the coupler type, with at leastone composition (B) containing, in a cosmetically suitable carrier, atleast one cosmetic oil in a total quantity from 10 to 80 wt % based onthe weight of composition (B), and hydrogen peroxide, wherein at leastone of the compositions (A) or (B) contains at least one4-morpholinomethyl-substituted silicone of formula (V),

in which

-   A denotes a structural unit (I), (II), or (III) bound via —O—

-   -   or an oligomeric or polymeric residue bound via —O— containing        structural units of formulas (I), (II), or (III), or half of an        oxygen atom connecting to a structural unit (III), or denotes        —OH,

-   * denotes a bond to one of the structural units (I), (II), or (III),    or denotes a terminal group B (Si-bound) or D (O-bound),

-   B denotes an —OH, —O—Si(CH₃)₃, —O—Si(CH₃)₂OH, —O—Si(CH₃)₂OCH₃ group,

-   D denotes an —H, —Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃ group,

-   a, b, and c denote integers from 0 to 990, with the provision that    a+b+c>0,

-   m, n, and o denote integers from 2 to 990.

Oxidative coloring agents preferred according to the present inventionare characterized in that they contain the at least one4-morpholinomethyl-substituted silicone of formula (V), which comprisesrespectively at least one of the structural units of formulas (I), (II),and (III), in a total quantity from about 0.001 to about 5 wt %,preferably about 0.005 to about 2 wt %, particularly preferably about0.01 to about 1 wt %, extraordinarily preferably about 0.1 to about 0.5wt %, based in each case on the total weight of the oxidative coloringagent.

In a first preferred embodiment the oxidative coloring agents accordingto the present invention and those preferred according to the presentinvention are characterized in that the at least one4-morpholinomethyl-substituted silicone of formula (V) is contained incomposition (A). A corresponding embodiment of the invention ischaracterized in that composition (A) contains at least one4-morpholinomethyl-substituted silicone of formula (V), that comprisesrespectively at least one of the structural units of formulas (I), (II),and (III), in a total quantity from about 0.002 to about 10 wt %,preferably about 0.001 to about 4 wt %, particularly preferably about0.02 to about 2 wt %, extraordinarily preferably about 0.2 to about 1.0wt %, based in each case on the total weight of composition (A).

In a further preferred embodiment, the oxidative coloring agentsaccording to the present invention and those preferred according to thepresent invention are characterized in that the at least one4-morpholinomethyl-substituted silicone of formula (V) is contained incomposition (B). A corresponding embodiment of the invention ischaracterized in that composition (B) contains at least one4-morpholinomethyl-substituted silicone of formula (V), that comprisesrespectively at least one of the structural units of formulas (I), (II),and (III), in a total quantity from about 0.002 to about 10 wt %,preferably about 0.001 to about 4 wt %, particularly preferably about0.02 to about 2 wt %, extraordinarily preferably about 0.2 to about 1.0wt %, based in each case on the total weight of composition (B).

Further oxidative coloring agents preferred according to the presentinvention are characterized in that they contain the at least one4-morpholinomethyl-substituted silicone of formula (V) in a formemulsified in water.

Particularly preferred oxidative coloring agents contain about 30 toabout 85 wt %, preferably about 40 to about 80 wt %, particularlypreferably about 50 to about 75 wt %, extraordinarily preferably about60 to about 70 wt % water, based in each case on the total weight of theoxidative coloring agent.

Particularly preferred oxidative coloring agents contain the at leastone 4-morpholinomethyl-substituted silicone of formula (V) in the formof an oil-in-water emulsion in which the number-average size of thesilicone particles in the emulsion is in the range from about 3 to about500 nm, preferably in the range from about 5 to about 60 nm.

Structural units of formulas (I), (II), and (III) can be presentstatistically distributed in the molecule, but the silicones usedaccording to the present invention can also be block copolymers made upof blocks of the individual structural units, in which context theblocks can in turn be present in statistically distributed fashion.

The * on the free valences of structural units (I), (II), or (III)denotes a bond to one of the structural units (I), (II), or (III) or aterminal group B (Si-bound) or D (O-bound).

The silicones used according to the present invention can betrimethylsilyl-terminated at both ends (D=—Si(CH₃)₃, B=—O—Si(CH₃)₃), butthey can also be dimethylsilylhydroxy- ordimethylsilylmethoxy-terminated at one or two ends. Silicones usedparticularly preferably in the context of the present invention have atleast one terminal dimethylsilylhydroxy group, i.e. are selected fromsilicones in which

B=—O—Si(CH₃)₂OH and D=—Si(CH₃)₃

B=—O—Si(CH₃)₂OH and D=—Si(CH₃)₂OH

B=—O—Si(CH₃)₂OH and D=—Si(CH₃)₂OCH₃

B=—O—Si(CH₃)₃ and D=—Si(CH₃)₂OH

B=—O—Si(CH₃)₂OCH₃ and D=—Si(CH₃)₂OH.

These silicones result in exorbitant improvements in the hair propertiesof the hair treated with the oxidative coloring agents according to thepresent invention and in accordance with the method according to thepresent invention, in particular in a tremendous decrease in contactangle.

In structural unit (III), residue A can denote

-   -   a structural unit (I), (II), or (III) bound via —O—, or    -   an oligomeric or polymeric residue bound via —O— containing        structural units of formulas (I), (II), and (III), or    -   half of an oxygen atom connecting to a structural unit (III), or        can denote —OH.

In the first case, structural unit (III) becomes one of the structuralunits (Ma), (IIIb), or (IIIc):

where m=n=o=1, and A resp. D are as defined above.

In the second case, in the formulas (IIIa), (IIIb), and (IIIc) recitedabove the indices m, n, and o can denote integers from 2 to 990. Thesecond case also, however, covers oligomeric or polymeric residues thatcontain at least two different structural units of formulas (I), (II),or (III), as depicted in formula (IIId):

in which a, b, and c denote integers from 0 to 990, with the provisionthat a+b+c>0, and n and o denote integers from 1 to 990.

In the third case, A denotes half of an oxygen atom connecting to astructural unit (III) (depicted in structural unit (IIIe)) or denotes—OH (depicted in structural unit (IIIf))

As already mentioned, the structural units of formulas (I), (II), and(III) can preferably be present in statistically distributed fashion.Pretreatment agents preferably used according to the present inventioncontain at least one 4-morpholinomethyl-substituted silicone of formula(V)

in which

-   A denotes a structural unit (I), (II), or (III) bound via —O—, or an    oligomeric or polymeric residue bound via —O— containing structural    units of formulas. (I), (II), or (III), or half of an oxygen atom    connecting to a structural unit (III), or denotes —OH,-   B denotes an —OH, —O—Si(CH₃)₃, —O—Si(CH₃)₂OH, —O—Si(CH₃)₂OCH₃ group,-   D denotes an —H, —Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃ group,-   a, b, and c denote integers from 0 to 990, with the provision that    a+b+c>0,-   n, and o denote integers from 1 to 990.

Structural formula (V) is intended to illustrate the fact that thesiloxane groups n and o do not obligatorily need to be bound directly toan end grouping B resp. D. Instead, in preferred formulas (V) a>0 orb>0, and in particularly preferred formulas (V) a>0 and b>0, i.e. theterminal grouping B resp. D is preferably bound to a dimethylsiloxygrouping. In formula (V) as well, the siloxane units a, b, c, n, and oare preferably statistically distributed.

The silicones represented by formula (V) and used according to thepresent invention can also be trimethylsilyl-terminated at both ends(D=—Si(CH₃)₃, B=—O—Si(CH₃)₃), but they can also be dimethylsilylhydroxy-or dimethylsilylmethoxy-terminated at one or two ends. Silicones usedparticularly preferably in the context of the present invention have atleast one terminal dimethylsilylhydroxy group, i.e. are selected fromsilicones in which

B=—O—Si(CH₃)₂OH and D=—Si(CH₃)₃

B=—O—Si(CH₃)₂OH and D=—Si(CH₃)₂OH

B=—O—Si(CH₃)₂OH and D=—Si(CH₃)₂OCH₃

B=—O—Si(CH₃)₃ and D=—Si(CH₃)₂OH

B=—O—Si(CH₃)₂OCH₃ and D=—Si(CH₃)₂OH.

These 4-morpholinomethyl-substituted silicones of formulas (V), whichrespectively comprise at least one of the structural units of formula(I), (II), and (III), result in surprisingly large improvements in thehair properties of the hair treated with the oxidative coloring agentsaccording to the present invention or in accordance with the methodaccording to the present invention, in particular in tremendouslyimproved hair protection and color protection in the context ofoxidative hair coloring.

In formula (V) as well, residue A can denote

-   -   a structural unit (I), (II), or (III) bound via —O—, or    -   an oligomeric or polymeric residue bound via —O— containing        structural units of formulas (I), (II), and (III), or    -   half of an oxygen atom connecting to a structural unit (III), or        can denote —OH.

By analogy with the statements regarding structural unit (III), formula(V) is thus refined to one of formulas (Va), (Vb), (Vc), (Vd), (Ve), or(Vf):

Structural unit (III) resp. the siloxane units o in formulas (V) can,via group A, constitute nest structures resp. partial cage structureswhen A denotes half of an oxygen atom connecting to a structural unit(III). Pretreatment agents according to the present invention thatcontain silicones having corresponding 4-morpholinomethyl-substitutedsilsesquioxane substructures are preferred according to the presentinvention, since these silicones result in enormously improved hairprotection in the context of oxidative coloring treatment.

Further oxidative coloring agents preferred according to the presentinvention are characterized in that they contain at least one4-morpholinomethyl-substituted silicone that comprises structural unitsof formula (VI)

in whichR1, R2, R3, and R4 mutually independently denote —H, —CH₃, a group D, astructural unit (I), (II), or (III), or an oligomeric or polymericresidue containing structural units of formulas (I), (II), or (III), ortwo of the residues R1, R2, R3, and R4 denote a structural unit—Si(R6)(R5)-, where

-   R5=—CH₃ or a structural unit of formula (I) or (II) or (III) or an    oligomeric or polymeric residue containing structural units of    formulas (I), (II), or (III),-   R6=—OH, —CH₃, or a structural unit of formula (I) or (II) or (III)    or an oligomeric or polymeric residue containing structural units of    formulas (I), (II), or (III).

In preferred silicones of formula (VI), at least one of the residues R1,R2, R3, or R4 denotes an oligomeric or polymeric residue containingstructural units of formulas (I), (II), or (III).

In further preferred silicones of formula (VI), at least one of theresidues R1, R2, R3, or R4 denotes an oligomeric or polymeric residuecontaining structural units of formulas (I) and (II).

In even further preferred silicones of formula (VI), at least one of theresidues R1, R2, R3, or R4 denotes an oligomeric or polymeric residuecontaining structural units of formulas (I) and (II) and (III).

At least one of the residues R1, R2, R3, or R4 preferably denotes an—[—Si(CH₃)₂—O]_(m) grouping, i.e. an oligomer resp. polymer ofstructural unit (I). In addition, preferably structural unit (II) resp.an oligomer or polymer thereof is never bound in the molecule alone, butrather always in a statistical distribution with further structuralunits of formula (I) as one of the residues R1, R2, R3, or R4.

Preferred silicones of formula (VI) can be described by formula (VI a)

in whichR1, R2, and R4 mutually independently denote —H, —CH₃, a group D, astructural unit (I), (II), or (III), or an oligomeric or polymericresidue containing structural units of formulas (I), (II), or (III), ortwo of the residues R1, R2, and R4 denote a structural unit—Si(R6)(R5)-, where

-   -   R5=—CH₃ or a structural unit of formula (I) or (II) or (III) or        an oligomeric or polymeric residue containing structural units        of formulas (I), (II), or (III),    -   R6=—OH, —CH₃, or a structural unit of formula (I) or (II)        or (III) or an oligomeric or polymeric residue containing        structural units of formulas (I), (II), or (III),

-   A denotes a structural unit (I), (II), or (III) bound via —O—, or an    oligomeric or polymeric residue bound via —O— containing structural    units of formulas (I), (II), or (III), or half of an oxygen atom    connecting to a structural unit (III), or denotes —OH,

-   D denotes an —H, —Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃ group,

-   a, b, and c denote integers from 0 to 990, with the provision that    a+b+c>0,

-   n, and o denote integers from 1 to 990.

Further preferred silicones of formula (VI) can be described by formula(VI b)

in which the residues and indices are as defined above.

Particularly preferred silicones of formula (VI) can be described byformula (VI c)

in which the residues and indices are as defined above, and the indicesd and e denote integers from 0 to 990.

In formulas (VI a), (VI b), and (VI c), at least one of the groupings Dpreferably denotes —Si(CH₃)₂OH.

The silsesquioxane structures can be even more pronounced in the4-morpholinomethyl-substituted silicones used according to the presentinvention, which intensifies the advantageous effects.

Particularly preferred oxidative coloring agents according to thepresent invention are characterized in that they contain at least one4-morpholinomethyl-substituted silicone that comprises structural unitsof formula (VII)

in which

-   A denotes a structural unit (I), (II), or (III) bound via —O—, or an    oligomeric or polymeric residue bound via —O— containing structural    units of formulas (I), (II), or (III), or half of an oxygen atom    connecting to a structural unit (III), or denotes —OH,-   D denotes an —H, —Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃ group,-   R denotes a 4-morpholinomethyl residue,-   R6 denotes —H or the grouping

where the siloxane units m, n, and o resp. a, b, c, x, and y are presentin statistically distributed fashion.

Particularly preferred oxidative coloring agents according to thepresent invention contain at least one silicone of the following formula(VII a)

with the definitions as for formula (VII).

Very particularly preferred oxidative coloring agents according to thepresent invention contain at least one silicone of the following formula(VII b)

with the definitions as for formula (VII).

In formulas (VII), (VII a), and (VII b), the bridging oxygen atomsbetween the morpholinomethyl-substituted silicon atoms can also besupplemented by an —[—Si(CH₃)₂—O]_(m) grouping, i.e. an oligomer orpolymer of structural unit (I). Corresponding oxidative coloring agentsaccording to the present invention are those which contain at least one4-morpholinomethyl-substituted silicone that comprises structural unitsof formula (VIII)

in which

-   A denotes a structural unit (I), (II), or (III) bound via —O—, or an    oligomeric or polymeric residue bound via —O— containing structural    units of formulas (I), (II), or (III), or half of an oxygen atom    connecting to a structural unit (III), or denotes —OH,-   D denotes an —H, —Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃ group,-   G1 to G9 mutually independently denote —O— or an -[—Si(CH₃)₂—O]_(m)    group where m=1 to 200,-   R denotes a 4-morpholinomethyl residue,-   R6 denotes —H or the grouping

where the siloxane units m, n, and o resp. a, b, c, x, and y are presentin statistically distributed fashion.

Particularly preferred oxidative coloring agents according to thepresent invention contain at least one silicone of the following formula(VIII a)

with the definitions as for formula (VIII).

Very particularly preferred oxidative coloring agents according to thepresent invention contain at least one silicone of the following formula(VIII b)

with the definitions as for formula (VIII).

Regardless of which special 4-morpholinomethyl-substituted silicone iscontained in the oxidative coloring agents according to the presentinvention, oxidative coloring agents according to the present inventionthat contain a 4-morpholinomethyl-substituted silicone in which morethan 50 mol % of the structural units are dimethylsiloxy units, i.e. inwhich structural unit (I) makes up at least half of all structural unitsof the silicone used, are preferred.

In other words, silicones in which m>(n+o) resp. (a+b+c)>(n+o), arepreferred.

Even further preferred oxidative coloring agents according to thepresent invention contain a 4-morpholinomethyl-substituted silicone inwhich more than about 87.5 mol % of the structural units aredimethylsiloxy units, i.e. in which structural unit (I) makes up morethan about 875 thousandths of all structural units of the silicone used.

In other words, silicones in which m>8(n+o) resp. (a+b+c)>8(n+o), arepreferred.

Even further preferred oxidative coloring agents according to thepresent invention contain a 4-morpholinomethyl-substituted silicone inwhich more than about 96 mol % of the structural units aredimethylsiloxy units, i.e. in which structural unit (I) makes up atleast ninety-six hundredths of all structural units of the siliconeused.

In other words, silicones in which m>25(n+o) resp. (a+b+c)>25(n+o), arepreferred.

Even further preferred oxidative coloring agents according to thepresent invention contain a 4-morpholinomethyl-substituted silicone inwhich more than about 98.7 mol % of the structural units aredimethylsiloxy units, i.e. in which structural unit (I) makes up atleast about nine hundred eighty-seven thousandths of all structuralunits of the silicone used.

In other words, silicones in which m>77(n+o) resp. (a+b+c)>77(n+o), arepreferred.

Even further preferred oxidative coloring agents according to thepresent invention contain a 4-morpholinomethyl-substituted silicone inwhich more than about 99.5 mol % of the structural units aredimethylsiloxy units, i.e. in which structural unit (I) makes up atleast nine hundred ninety-five thousandths of all structural units ofthe silicone used.

In other words, silicones in which m>200(n+o) resp. (a+b+c)>200(n+o),are preferred.

In summary, preferred oxidative coloring agents according to the presentinvention are characterized in that they contain at least one4-morpholinomethyl-substituted silicone in which

m>(n+o) resp. (a+b+c)>(n+o), preferably

m>8(n+o) resp. (a+b+c)>8(n+o), particularly preferably

m>25(n+o) resp. (a+b+c)>25(n+o), more preferably

m>77(n+o) resp. (a+b+c)>77(n+o), and in particular

m>200(n+o) resp. (a+b+c)>200(n+o).

Further oxidative coloring agents preferred according to the presentinvention are characterized in that hydroxy-terminated4-morpholinomethyl-substituted silicone(s) in which the molar ratio ofhydroxy to alkoxy is in the range from about 0.2:1 to about 0.4:1,preferably in the range from about 1:0.8 to about 1:1.1, is/arecontained.

Further oxidative coloring agents preferred according to the presentinvention are characterized in that the weight-average molar mass of the4-morpholinomethyl-substituted silicone of formula (V) used in step a isin the range from about 2000 to about 1,000,000 gmol⁻¹, preferably inthe range from about 5000 to about 200,000 gmol⁻¹.

The average molar masses of amino-substituted silicones are measurable,for example, by gel permeation chromatography (GPC) at room temperaturein polystyrene. Styragel μ columns can be selected as columns, THF as aneluent, and 1 ml/min as a flow rate. Detection is accomplishedpreferably by refractometry using a UV meter.

4-Morpholinomethyl-substituted silicones of formula (V) that areparticularly preferred according to the present invention are containedin the raw material Belsil ADM 8301 E (ex Wacker Silicones) under thename Amodimethicone/Morpholinomethyl Silsesquioxane. Belsil ADM 8301 Erepresents a microemulsion and is made up of the followingconstituents:Amodimethicone/Morpholinomethyl Silsesquioxane (10 wt %);Trideceth-5 (about 5 wt %); glycerol (about 2.5 wt %); phenoxyethanol(about 0.45 wt %); and water (about 82.05 wt %).

It has become apparent that the oxidative coloring agents according tothe present invention can be further improved if specific nonioniccomponents are likewise contained in the pretreatment agents usedaccording to the present invention. These nonionic components moreoverhave positive effects on the shelf stability of the oxidative coloringagents according to the present invention. Nonionic components that areparticularly suitable here are ethoxylates of decanol, undecanol,dodecanol, tridecanol, myristyl alcohol, cetyl alcohol, and/or stearylalcohol. Ethoxylated tridecanols have proven to be particularlysuitable, and are incorporated with particular preference into theoxidative coloring agents according to the present invention. Branchedethoxylated tridecanols are particularly preferred, in particularbranched tridecanols having 3 to 5 ethylene oxide units in the molecule.Oxidative coloring agents particularly preferred according to thepresent invention contain, based in each case on their weight, about0.001 to about 5 wt %, preferably about 0.005 to about 3.5 wt %,particularly preferably about 0.01 to about 2 wt %, more preferablyabout 0.05 to about 1 wt %, and in particular about 0.1 to about 0.5 wt% branched ethoxylated tridecanol, particularly preferably about 0.001to about 5 wt %, preferably about 0.005 to about 3.5 wt %, particularlypreferably about 0.01 to about 2 wt %, more preferably about 0.05 toabout 1 wt %, and in particular about 0.1 to about 0.5 wt % branchedethoxylated tridecanol having 3 to 5 ethylene oxide units in themolecule.

The oxidative coloring agents according to the present invention cancontain further ingredients. It is preferred in this context to usepolyvalent alcohols that have moisture-donating properties. Oxidativecoloring agents according to the present invention that contain at leastone polyvalent alcohol, preferably selected from the group of sorbitoland/or glycerol and/or 1,2-propylene glycol or mixtures thereof, in atotal quantity from about 0.05 to about 15 wt %, preferably about 0.1 toabout 10 wt %, particularly preferably about 0.15 to about 5 wt %, andin particular about 0.15 to about 1 wt %, based in each case on theweight of the oxidative coloring agent, are preferred here. For specificutilization sectors it can be advantageous to use only one of the threeaforementioned preferred polyvalent alcohols. In most cases, glycerol ispreferred. Mixtures of two of the three polyvalent alcohols, or of allthree polyvalent alcohols, can nevertheless be preferred in otherutilization sectors. A mixture of glycerol, sorbitol, and 1,2-propyleneglycol at a weight ratio of about 1:(0.5-1):(0.1-0.5) has provenparticularly advantageous here.

Besides sorbitol, glycerol, and 1,2-propylene glycol, further polyvalentalcohols that are suitable are those having at least 2 OH groups,preferably mannitol, xylitol, polyethylene glycol, polypropylene glycol,and mixtures thereof. Among these compounds those having 2 to 12 OHgroups, and in particular those having 2,3,4, 5, 6, or 10 OH groups, arepreferred.

Polyhydroxy compounds having 2 OH groups are, for example, glycol(CH₂(OH)CH₂OH) and other 1,2-diols such as H—(CH₂)_(n)—CH(OH)CH₂OH wheren=2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.1,3-Diols such as H—(CH₂)_(n)—CH(OH)CH₂CH₂OH, where n=1, 2, 3, 4, 5, 6,7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, are also usableaccording to the present invention. The (n,n+1)-resp. (n,n+2)-diolshaving non-terminal OH groups can likewise be used. Importantrepresentatives of polyhydroxy compounds having 2 OH groups are also thepolyethylene and polypropylene glycols. Further preferred polyvalentalcohols that can be used are, for example, xylitol, propylene glycols,polyethylene glycols, in particular those having average molecularweights from 200 to 800. It is particularly preferred to use glycerol,so that agents that contain no other polyvalent alcohols besidesglycerol are particularly preferred.

The use of specific care-providing substances in the oxidative coloringagents according to the present invention is preferred in terms of afurther reduction in hair damage due to the oxidative coloringtreatment.

Oxidative coloring agents preferred according to the present inventionare characterized in that they additionally contain care-providingsubstance(s) in a total quantity from about 0.001 to about 10 wt %,preferably about 0.005 to about 7.5 wt %, particularly preferably about0.01 to about 5 wt %, and in particular about 0.05 to about 2.5 wt %,based in each case on the total weight of the oxidative coloring agent.Preferred care-providing substance(s) are selected from at least one ofthe groups recited below:

i. L-carnitine and/or salts thereof;

ii. taurine and/or salts thereof;

iii. niacinamide;

iv. ubiquinone;

v. ectoin;

vi. vitamins;

vii. flavonoids.

Oxidative coloring agents preferred according to the present inventioncan contain one or more amino acids as a further ingredient. Amino acidsusable particularly preferably according to the present invention derivefrom the group of glycine, alanine, valine, leucine, isoleucine,phenylalanine, tyrosine, tryptophan, proline, aspartic acid, glutamicacid, asparagine, glutamine, serine, threonine, cysteine, methionine,lysine, arginine, histidine, β-alanine, 4-aminobutyric acid (GABA),betaine, L-cystine, L-carnitine, L-citrulline, L-theanine,3′,4′-dihydroxy-L-phenylalanine (L-DOPA), 5′-hydroxy-L-tryptophan,L-homocysteine, S-methyl-L-methionine, S-allyl-L-cysteine sulfoxide(L-alliine), L-trans-4-hydroxyproline, L-5-oxoproline (L-pyroglutamicacid), L-phosphoserine, creatine, 3-methyl-L-histidine, L-ornithine;both the individual amino acids and mixtures can be used.

Preferred oxidative coloring agents according to the present inventioncontain one or more amino acids in narrower quantity ranges. Oxidativecoloring agents preferred according to the present invention arecharacterized here in that they contain as a care-providing substanceabout 0.01 to about 5 wt %, preferably about 0.02 to about 2.5 wt %,particularly preferably about 0.05 to about 1.5 wt %, more preferablyabout 0.075 to about 1 wt %, and in particular about 0.1 to about 0.25wt % amino acid(s), preferably from the group of glycine and/or alanineand/or valine and/or lysine and/or leucine and/or threonine, based ineach case on the total weight of the oxidative coloring agent.

The oxidative coloring agent according to the present invention can beformulated as a water-based emulsion, a spray, a cream, gel, lotion,paste, or shampoo.

Composition (B) used as part of the oxidative coloring agent accordingto the present invention contains as a first obligatory ingredient atleast one oxidizing agent. Preferred oxidizing agents are selected fromperoxo compounds, preferably selected from hydrogen peroxide, a solidaddition compound of hydrogen peroxide with inorganic or organiccompounds, such as sodium perborate, sodium percarbonate, magnesiumpercarbonate, sodium percarbamide, polyvinylpyrrolidone.nH₂O₂ (n is apositive number greater than 0), urea peroxide, and melamine peroxide,furthermore selected from diammonium peroxodisulfate (also referred toas ammonium persulfate), disodium peroxodisulfate (also referred to assodium persulfate), and dipotassium peroxodisulfate (also referred to aspotassium persulfate), and from mixtures of these oxidizing agents.Oxidizing agents used with very particular preference according to thepresent invention are aqueous hydrogen peroxide solutions. Theconcentration of a hydrogen peroxide solution is determined on the onehand by regulatory provisions and on the other hand by the desiredeffect; 6- to 12-weight-percent solutions in water are preferably used.Oxidative coloring agents preferred according to the present inventionare characterized in that the composition (B) used to manufacture themcontains, based on its weight, about 1 to about 24 wt %, preferablyabout 4 to about 10 wt %, particularly preferably about 3 to about 6 wt% hydrogen peroxide (calculated as 100% H₂O₂).

For oxidative hair coloring methods, it is usual that shortly beforeapplication into the hair, the coloring composition (A), which containsone or more oxidation dye precursors and optionally one or moresubstantive dyes, is mixed with an aqueous oxidizing-agent-containingcomposition (B) to yield the ready-to-use oxidative coloring agent(according to the present invention), and is then applied onto the hair.The coloring composition (A) and the oxidizing-agent-containingcomposition (B) are usually coordinated with one another in such a waythat with a mixing ratio of about 1 to about 1 (based on parts byweight) an initial concentration of hydrogen peroxide from about 0.5 toabout 12 wt %, preferably about 2 to about 10 wt %, particularlypreferably about 3 to about 6 wt % hydrogen peroxide (calculated as 100%H₂O₂) is present in the hair coloring agent, based on the weight of theoxidative coloring agent. It is, however, equally possible to coordinatethe coloring composition (A) and the oxidizing-agent-containingcomposition (B) with one another in such a way that the concentrationsnecessary in the ready-to-use oxidative coloring agent are obtained bymeans of mixing ratios other than about 1:1, for example by aweight-related mixing ratio of about 1:2 or about 1:3 or even about 2:3.Oxidative coloring agents preferred according to the present inventionare characterized in that they contain an initial quantity of hydrogenperoxide from about 0.5 to about 12 wt %, preferably about 2 to about 10wt %, particularly preferably about 3 to about 6 wt % hydrogen peroxide(calculated as 100% H₂O₂), based in each case on the weight of theoxidative coloring agent.

Further oxidative coloring agents preferred according to the presentinvention are characterized in that they contain at least one cosmeticoil in a total quantity from about 5 to about 50 wt %, preferably about8 to about 40 wt %, particularly preferably about 12 to about 30 wt %,extraordinarily preferably about 15 to about 25 wt %, based in each caseon the weight of the oxidative coloring agent.

Oxidative coloring processes on keratin fibers usually proceed in analkaline environment. In order to minimize stress on the keratin fibersand also on the skin, however, it is not desirable to establish too higha pH. It is therefore preferred if the pH of the oxidative coloringagent preferred according to the present invention is between about 7and about 11, in particular in the range from about 8 to about 10.5. ThepH values for purposes of the present invention are pH values that havebeen measured at a temperature of 22° C.

The alkalizing agents usable according to the present invention in orderto establish the preferred pH can be selected from the group of ammonia,basic amino acids, alkali hydroxides, alkanolamines; alkali metalmetasilicates, alkali phosphates, and alkali hydrogen phosphates.Lithium, sodium, potassium preferably serve as alkali metal ions, inparticular sodium or potassium.

The basic amino acids usable as alkalizing agents are preferablyselected from the group of L-arginine, D-arginine, D,L-arginine,L-lysine, D-lysine, D,L-lysine, particularly preferably L-arginine,D-arginine, D,L-arginine used as an alkalizing agent for purposes of theinvention.

The alkali hydroxides usable as alkalizing agents are preferablyselected from the group of sodium hydroxide and potassium hydroxide.

The alkanolamines usable as alkalizing agents are preferably selectedfrom primary amines having a C₂ to C₆ alkyl basic structure that carriesat least one hydroxyl group. Particularly preferred alkanolamines areselected from the group that is constituted from 2-aminoethan-1-ol(monoethanolamine), 3-aminopropan-1-ol, 4-aminobutan-1-ol,5-aminopentan-1-ol, 1-aminopropan-2-ol, 1-aminobutan-2-ol,1-aminopentan-2-ol, 1-aminopentan-3-ol, 1-aminopentan-4-ol,3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol,3-aminopropane-1,2-diol, 2-amino-2-methylpropane-1,3-diol. Alkanolaminesvery particularly preferred according to the present invention areselected from the group of: 2-aminoethan-1-ol,2-amino-2-methylpropan-1-ol, and 2-amino-2-methylpropane-1,3-diol.

The use of hydrogen peroxide or addition products thereof with organicresp. inorganic compounds is often insufficient for a coloring operationthat requires considerable lightening of very dark hair. A combinationof hydrogen peroxide and peroxodisulfate salts (persulfate salts) isgenerally used in such cases. Preferred persulfate salts are ammoniumperoxydisulfate, potassium peroxydisulfate, sodium peroxydisulfate, andmixtures thereof.

The at least one persulfate salt is contained preferably in a totalquantity from about 0.1 to about 25 wt %, particularly preferably in atotal quantity from about 1 to about 15 wt %, based on the weight of theoxidative coloring agent according to the present invention.

The composition (B) used to manufacture the oxidative coloring agentaccording to the present invention contains as a further obligatorycomponent at least one cosmetic oil in a total quantity from about 10 toabout 80 wt %, based on the weight of composition (B). The cosmetic oilis liquid under standard conditions (20° C., 1013.25 mbar); essentialoils and perfume oils resp. fragrances are not included among thecosmetic oils. The cosmetic oils that are liquid under standardconditions are not miscible with water. “Essential oils” are understoodaccording to the present invention as mixtures of volatile componentsthat are produced by steam distillation from vegetable raw materials,e.g. citrus oils. When a “cosmetic oil” is discussed in the presentapplication, this always refers to a cosmetic oil that is not afragrance and not an essential oil, is liquid under standard conditions,and is not miscible with water.

The definition of a “fragrance” for purposes of the present applicationcorresponds to the definition usual in the art, as may be gathered fromthe RÖMPP Chemie Lexikon [Chemical Lexicon] as of December 2007.According to the latter, a fragrance is a chemical compound having anodor and/or taste that excites the receptors of the hair cells of theolfactory system (adequate stimulus). The physical and chemicalproperties necessary for this are a low molar mass of at most about 300g/mol, a high vapor pressure, minimal water solubility and high lipidsolubility, as well as weak polarity and the presence of at least oneosmophoric group in the molecule. In order to distinguish volatilelow-molecular-weight substances that are usually (and also for purposesof the present application) viewed and utilized not as fragrances butinstead principally as solvents, for example ethanol, propanol,isopropanol, and acetone, from fragrances according to the presentinvention, fragrances according to the present invention have a molarmass from about 74 to about 300 g/mol, contain at least one osmophoricgroup in the molecule, and have an odor and/or taste, i.e. they excitethe receptors of the hair cells of the olfactory system.

Cosmetic oils preferred according to the present invention are selectedfrom natural and synthetic hydrocarbons, particularly preferably fromparaffin oils, C₁₈ to C₃₀ isoparaffins, in particular isoeicosane,polyisobutenes, and polydecenes, which are obtainable, for example,under the name Emery® 3004, 3006, 3010 or under the name Ethylflo® fromAlbemarle or Nexbase® 2004G from Nestle, further selected from C₈ to C₁₆isoparaffins, in particular from isodecane, isododecane, isotetradecane,and isohexadecane as well as mixtures thereof, as well as1,3-di-(2-ethylhexyl)cyclohexane (obtainable e.g. under the trade nameCetiol® S from BASF).

Further cosmetic oils preferred according to the present invention areselected from benzoic acid esters of linear or branched C₈₋₂₂ alkanols.Benzoic acid C₁₂ to C₁₅ alkyl esters, obtainable e.g. as the commercialproduct Finsolv® TN, benzoic acid isostearyl esters, obtainable e.g. asthe commercial product Finsolv® SB, ethylhexyl benzoate, obtainable e.g.as the commercial product Finsolv® EB, and benzoic acid octyldodecylesters, obtainable e.g. as the commercial product Finsolv® BOD, areparticularly preferred.

Further cosmetic oils preferred according to the present invention areselected from fatty alcohols having 6 to 30 carbon atoms, which areunsaturated or branched and saturated or branched and unsaturated. Thebranched alcohols are often also referred to as “Guerbet alcohols,”since they are obtainable via the Guerbet reaction. Preferred alcoholoils are 2-hexyldecanol (Eutanol® G 16), 2-octyldodecanol (Eutanol® G),2-ethyhexyl alcohol, and isostearyl alcohol.

Further preferred cosmetic oils are selected from mixtures of Guerbetalcohols and Guerbet alcohol esters, e.g. the commercial product Cetiol®PGL (2-hexyldecanol and 2-hexyldecyl laurate).

Further cosmetic oils preferred according to the present invention areselected from triglycerides (=triesters of glycerol) of linear orbranched, saturated or unsaturated, optionally hydroxylated C₈₋₃₀ fattyacids. The use of natural oils, e.g. amaranth seed oil, apricot kerneloil, argan oil, avocado oil, babassu oil, cottonseed oil, borage seedoil, camelina oil, thistle oil, peanut oil, pomegranate seed oil,grapefruit seed oil, hemp oil, hazelnut oil, elderberry seed oil,blackcurrant seed oil, jojoba oil, linseed oil, macadamia nut oil, cornoil, almond oil, marula oil, evening primrose oil, olive oil, palm oil,palm kernel oil, para nut oil, pecan nut oil, peach kernel oil, rapeseedoil, castor oil, sea buckthorn pulp oil, sea buckthorn seed oil, sesameoil, soy oil, sunflower oil, grapeseed oil, walnut oil, wild rose oil,wheat germ oil, and the liquid components of coconut oil and the like,can be particularly preferred. Synthetic triglyceride oils are alsopreferred, however, in particular Capric/Caprylic Triglycerides, e.g.the commercial products Myritol® 318, Myritol® 331 (BASF), or Miglyol®812 (Hüls) having unbranched fatty acid esters, as well as glyceryltriisostearine having branched fatty acid esters.

Further cosmetic oils particularly preferred according to the presentinvention are selected from dicarboxylic acid esters of linear orbranched C₂ to C₁₀ alkanols, in particular diisopropyl adipate,di-n-butyl adipate, di-(2-ethylhexyl) adipate, dioctyl adipate,diethyl-/di-n-butyl/dioctyl sebacate, diisopropyl sebacate, dioctylmalate, dioctyl maleate, dicaprylyl maleate, diisooctyl succinate,di-2-ethylhexyl succinate, and di-(2-hexyldecyl) succinate.

Further cosmetic oils particularly preferred according to the presentinvention are selected from esters of linear or branched, saturated orunsaturated fatty alcohols having 2 to 30 carbon atoms with linear orbranched, saturated or unsaturated fatty acids having 2 to 30 carbonatoms, which can be hydroxylated. These include 2-hexyldecyl stearate(Eutanol® G 16 S), 2-hexyldecyl laurate, isodecyl neopentanoate,isononyl isononanoate, 2-ethylhexyl palmitate (Cegesoft® C 24), and2-ethylhexyl stearate (Cetiol® 868). Also preferred are isopropylmyristate, isopropyl palmitate, isopropyl stearate, isopropylisostearate, isopropyl oleate, isooctyl stearate, isononyl stearate,isocetyl stearate, isononyl isononanoate, isotridecyl isononanoate,cetearyl isononanoate, 2-ethylhexyl laurate, 2-ethylhexyl isostearate,2-ethylhexyl cocoate, 2-octyldodecyl palmitate, butyl octanoic acid2-butyl octanoate, diisotridecyl acetate, n-butyl stearate, n-hexyllaurate, n-decyl oleate, oleyl oleate, oleyl erucate, erucyl oleate,erucyl erucate, ethylene glycol dioleate, and ethylene glycoldipalmitate.

Further cosmetic oils preferred according to the present invention areselected from addition products of 1 to 5 propylene oxide units withmono- or polyvalent C₈₋₂₂ alkanols such as octanol, decanol, decanediol,lauryl alcohol, myristyl alcohol, and stearyl alcohol, e.g. PPG-2Myristyl Ether and PPG-3 Myristyl Ether (Witconol® APM).

Further cosmetic oils preferred according to the present invention areselected from addition products of at least 6 ethylene oxide and/orpropylene oxide units with mono- or polyvalent C₃₋₂₂ alkanols such asglycerol, butanol, butanediol, myristyl alcohol, and stearyl alcohol,which can be esterified if desired, e.g. PPG-14 Butyl Ether (Ucon Fluid®AP), PPG-9 Butyl Ether (Breox® B25), PPG-10 Butanediol (Macol® 57),PPG-15 Stearyl Ether (Arlamol® E), and glycereth-7 diisonoanoate.

Further cosmetic oils preferred according to the present invention areselected from C₈ to C₂₂ fatty alcohol esters of monovalent or polyvalentC₂ to C₇ hydroxycarboxylic acids, in particular the esters of glycolicacid, lactic acid, malic acid, tartaric acid, citric acid, and salicylicacid. Such esters based on linear C_(14/15) alkanols, e.g. C₁₂ to C₁₅alkyl lactate, and on C_(12/13) alkanols branched in the 2-position, canbe obtained under the trade name Cosmacol® from Nordmann, Rassmann GmbH& Co., Hamburg, in particular the commercial products Cosmacol® ESI,Cosmacol® EMI, and Cosmacol® ETI.

Further cosmetic oils preferred according to the present invention areselected from symmetrical, asymmetrical, or cyclic esters of carbonicacid with C₃₋₂₂ alkanols, C₃₋₂₂ alkanediols, or C₃₋₂₂ alkanetriols, e.g.dicaprylyl carbonate (Cetiol® CC), or the esters according to theteaching of DE 19756454 A1, in particular glycerol carbonate.

Further cosmetic oils that can be preferred according to the presentinvention are selected from esters of dimers of unsaturated C₁₂ to C₂₂fatty acids (dimer fatty acids) with monovalent linear, branched, orcyclic C₂ to C₁₈ alkanols or with polyvalent linear or branched C₂ to C₆alkanols.

Further cosmetic oils that are suitable according to the presentinvention are selected from among the silicone oils that include, forexample, dialkyl- and alkylarylsiloxanes such as e.g.cyclopentasiloxane, cyclohexasiloxane, dimethylpolysiloxane, andmethyphenylpolysiloxane, but also hexamethyldisiloxane,octamethyltrisiloxane, and decamethyltetrasiloxane. Volatile siliconeoils, which can be cyclic, can be preferred, for exampleoctamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, anddodecamethylcyclohexasiloxane, as well as mixtures thereof such as thosecontained, for example, in the commercial products DC 244, 245, 344, and345 of Dow Corning. Also suitable are volatile linear silicone oils, inparticular hexamethyldisiloxane (L₂), octamethyltrisiloxane (L₃),decamethyltetrasiloxane (L₄), as well as any mixtures of two or three ofL₂, L₃, and/or L₄, preferably mixtures such as those contained e.g. inthe commercial products DC 2-1184, Dow Corning° 200 (0.65 cSt), and DowCorning° 200 (1.5 cSt) of Dow Corning. Preferred nonvolatile siliconeoils are selected from higher-molecular-weight lineardimethylpolysiloxanes, obtainable commercially e.g. under the name DowCorning® 190, Dow Corning° 200 Fluid, having kinematic viscosities (25°C.) in the range from about 5 to about 100 cSt, preferably about 5 toabout 50 cSt, or even about 5 to about 10 cSt, and dimethylpolysiloxanehaving a kinematic viscosity (25° C.) of approximately about 350 cSt.

It can be extraordinarily preferred according to the present inventionto use mixtures of the aforementioned cosmetic oils.

Preferred compositions (B) used according to the present invention arecharacterized in that the cosmetic oil is selected from natural andsynthetic hydrocarbons, particularly preferably from paraffin oils, C₁₈to C₃₀ isoparaffins, in particular isoeicosane, polyisobutenes, andpolydecenes, C₈ to C₁₆ isoparaffins, and1,3-di-(2-ethylhexyl)cyclohexane; benzoic acid esters of linear orbranched C₈₋₂₂ alkanols; fatty alcohols having 6 to 30 carbon atoms,which are unsaturated or branched and saturated or branched andunsaturated; triglycerides of linear or branched, saturated orunsaturated, optionally hydroxylated C₈₋₃₀ fatty acids, in particularnatural oils; dicarboxylic acid esters of linear or branched C₂ to C₁₀alkanols; esters of linear or branched, saturated or unsaturated fattyalcohols having 2 to 30 carbon atoms with linear or branched, saturatedor unsaturated fatty acids having 2 to 30 carbon atoms, which can behydroxylated; addition products of 1 to 5 propylene oxide units withmono- or polyvalent C₈₋₂₂ alkanols; addition products of at least 6ethylene oxide and/or propylene oxide units with mono- or polyvalentC₃₋₂₂ alkanols; C₈ to C₂₂ fatty alcohol esters of monovalent orpolyvalent C₂ to C₇ hydroxycarboxylic acids; symmetrical, asymmetrical,or cyclic esters of carbonic acid with C₃₋₂₂ alkanols, C₃₋₂₂alkanediols, or C₃₋₂₂ alkanetriols; esters of dimers of unsaturated C₁₂to C₂₂ fatty acids (dimer fatty acids) with monovalent linear, branched,or cyclic C₂ to C₁₈ alkanols or with polyvalent linear or branched C₂ toC₆ alkanols; silicone oils; and mixtures of the aforementionedsubstances.

Preferred oxidative coloring agents according to the present inventionare characterized in that the composition (B) used to manufacture themcontains at least one cosmetic oil in a total quantity from about 12 toabout 70 wt %, preferably about 14 to about 60 wt %, particularlypreferably about 15 to about 52 wt %, and extraordinarily preferablyabout 17 to about 35 wt %, based in each case on the weight ofcomposition (B).

Further preferred oxidative coloring agents according to the presentinvention are characterized in that the composition (B) used accordingto the present invention contains at least one surfactant.

When selecting surfactants suitable according to the present invention,it is particularly preferred to use a mixture of surfactants in order toallow optimum adjustment of the stability of the oxidizing agentcompositions (B) used according to the present invention.

Preferred oxidative coloring agents according to the present inventionare characterized in that the surfactant contained in composition (B) isselected from nonionic surfactants and anionic surfactants and frommixtures thereof. Nonionic surfactants used with particular preferenceare selected from castor oil ethoxylated with about 20 to about 100 molethylene oxide per mol, ethoxylated C₈ to C₂₄ alkanols having about 10to about 100 mol ethylene oxide per mol, ethoxylated C₈ to C₂₄carboxylic acids having about 10 to about 100 mol ethylene oxide permol, sorbitan monoesters, ethoxylated with about 20 to about 100 molethylene oxide per mol, of linear saturated and unsaturated C₁₂ to C₃₀carboxylic acids, which can be hydroxylated, in particular those ofmyristic acid, palmitic acid, stearic acid, or mixtures of these fattyacids, alkylmono- and -oligoglycosides having 8 to 22 carbon atoms inthe alkyl residue and ethoxylated analogs thereof, and mixtures of theaforesaid substances.

Castor oil ethoxylated with about 40 to about 80 mol ethylene oxide permol is preferably contained in the compositions (B) preferably usedaccording to the present invention.

The ethoxylated C₈ to C₂₄ alkanols have the formula R¹O(CH₂CH₂O)_(n)H,where R¹ denotes a linear or branched alkyl residue and/or alkenylresidue having 8 to 24 carbon atoms, and n (the average number ofethylene oxide units per molecule) denotes numbers from 10 to 100,preferably 10 to 30, particularly preferably 15 to 25 mol ethylene oxideper 1 mol caprylyl alcohol, 2-ethylhexyl alcohol, capryl alcohol, laurylalcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol,palmitoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol,elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleylalcohol, behenyl alcohol, erucyl alcohol, and brassidyl alcohol, as wellas industrial mixtures thereof. Adducts of about 10 to about 100 molethylene oxide with industrial fatty alcohols having 12 to 18 carbonatoms, for example coconut, palm, palm kernel, or tallow fatty alcohol,are also suitable. Laureth-10, Laureth-12, Laureth-15, Laureth-20,Laureth-30, Myreth-10, Myreth-12, Myreth-15, Myreth-20, Myreth-30,Ceteth-10, Ceteth-12, Ceteth-15, Ceteth-20, Ceteth-30, Steareth-10,Steareth-12, Steareth-15, Steareth-20, Steareth-30, Oleth-10, Oleth-12,Oleth-15, Oleth-20, Oleth-30, Ceteareth-10, Ceteareth-15, Ceteareth-12,Ceteareth-15, Ceteareth-20, Ceteareth-30, as well as Coceth-10,Coceth-12, Coceth-15, Coceth-20, and Coceth-30, are particularlypreferred.

The ethoxylated C₈ to C₂₄ carboxylic acids have the formulaR¹O(CH₂CH₂)_(n)H, where R¹O denotes a linear or branched, saturated orunsaturated acyl residue having 8 to 24 carbon atoms and n (the averagenumber of ethylene oxide units per molecule) denotes numbers from 10 to100, preferably 10 to 30 mol ethylene oxide per 1 mol caprylic acid,2-ethylhexanoic acid, capric acid, lauric acid, isotridecanoic acid,myristic acid, cetylic acid, palmitoleic acid, stearic acid, isostearicacid, oleic acid, elaidic acid, petroselic acid, arachidic acid,gadoleic acid, behenic acid, erucic acid, and brassidic acid, as well asindustrial mixtures thereof. Adducts of 10 to 100 mol ethylene oxidewith industrial fatty acids having 12 to 18 carbon atoms, for examplecoconut, palm, palm kernel, or tallow fatty acid, are also suitable.PEG-50 monostearate, PEG-100 monostearate, PEG-50 monooleate, PEG-100monooleate, PEG-50 monolaurate, and PEG-100 monolaurate are particularlypreferred.

Preferred sorbitan monoesters, ethoxylated with about 20 to about 100mol ethylene oxide per mol, of linear saturated and unsaturated C₁₂ toC₃₀ carboxylic acids, which can be hydroxylated, are selected fromPolysorbate-20, Polysorbate-40, Polysorbate-60, and Polysorbate-80.

C₈ to C₂₂ alkylmono- and -oligoglycosides are also preferably used. C₈to C₂₂ alkylmono- and -oligoglycosides represent known, commerciallyusual surfactants and emulsifier agents. They are manufactured inparticular by reacting glucose or oligosaccharides with primary alcoholshaving 8 to 22 carbon atoms. With regard to the glycoside residue, bothmonoglycosides in which a cyclic sugar residue is bound glycosidicallyto the fatty alcohol, and oligomeric glycosides having a degree ofoligomerization up to approximately 8, preferably 1 to 2, are suitable.The degree of oligomerization is a statistical average that is based ona homolog distribution that is usual for industrial products of thiskind. Products that are obtainable under the name Plantacare® contain aglucosidically bound C₈ to C₁₆ alkyl group on an oligoglucoside residuewhose average degree of oligomerization is 1 to 2, in particular 1.2 to1.4. Particularly preferred C₈ to C₂₂ alkyl mono- and -oligoglycosidesare selected from octyl glucoside, decyl glucoside, lauryl glucoside,palmityl glucoside, isostearyl glucoside, stearyl glucoside, arachidylglucoside, and behenyl glucoside, as well as mixtures thereof. The acylglucamides derived from glucamine are also suitable as nonionicoil-in-water emulsifier agents.

Anionic surfactants suitable in the compositions (B) used according tothe present invention are all anionic surface-active substances suitablefor use on the human body, which comprise an anionic group impartingwater solubility, for example a carboxylate, sulfate, sulfonate, orphosphate group, and a lipophilic alkyl group having approximately 8 to30 carbon atoms, preferably 8 to 24 carbon atoms, in the molecule.Glycol ether or polyglycol ether groups, ester, ether, and amide groups,and hydroxyl groups can additionally be contained in the molecule.Examples of suitable anionic surfactants are, in each case in the formof the sodium, potassium, and ammonium salts and the mono-, di, andtrialkanolammonium salts having 2 to 4 carbon atoms in the alkanolgroup: linear and branched fatty acids having 8 to 30 carbon atoms(soaps), polyethoxylated ethercarboxylic acids, acyl sarcosides, acyltaurides, acyl isethionates, sulfosuccinic acid mono- and dialkyl estersand sulfosuccinic acid monoalkylpolyoxyethyl esters having 1 to 6ethylene oxide groups, linear alkanesulfonates, linearalpha-olefinsulfonates, sulfonates of unsaturated fatty acids having upto 6 double bonds, alpha-sulfo fatty acid methyl esters of fatty acids,C₈ to C₂₀ alkyl sulfates and C₈ to C₂₀ alkyl ether sulfates having up to15 oxyethyl groups, mixtures of surface-active hydroxysulfonates,sulfated hydroxyalkyl polyethylene glycol ethers and/or hydroxyalkylenepropylene glycol ethers, esters of tartaric acid or citric acid withethoxylated or propoxylated fatty alcohols, optionally polyethoxylatedalkyl and/or alkenyl ether phosphates, sulfated fatty acid alkyleneglycol esters, as well as monoglyceride sulfates and monoglyceride ethersulfates.

Preferred anionic surfactants are soaps, C₈ to C₂₀ alkyl sulfates, C₈ toC₂₀ alkyl ether sulfates, and C₈ to C₂₀ ether carboxylic acids having 8to 20 carbon atoms in the alkyl group and up to 12 ethylene oxide groupsin the molecule. Sodium cetearyl sulfate is particularly preferred.

Preferably the total quantity of at least one surfactant in theoxidizing agent composition (B) is about 0.1 to about 5 wt %, preferablyabout 0.5 to about 3 wt %, and particularly preferably about 1 to about2 wt %, based in each case on the total weight of the oxidizing agentcomposition (B).

Particularly preferably, the oxidizing agent composition (B) usedaccording to the present invention contains a total of about 0.1 toabout 5 wt %, preferably about 0.5 to about 3 wt %, and particularlypreferably about 1 to about 2 wt %, of a mixture of nonionic and anionicsurfactants, based in each case on the total weight of the oxidizingagent composition (B).

Further preferred oxidative coloring agents according to the presentinvention are characterized in that the composition (B) used accordingto the present invention contains at least one linear saturated alkanolhaving 12 to 30 carbon atoms.

Preferred linear saturated alkanols having 12 to 30 carbon atoms, inparticular having 16 to 22 carbon atoms, are selected from cetylalcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, andlanolin alcohol, as well as mixtures of these alkanols. Alkanol mixturesparticularly preferred according to the present invention are thoseobtainable upon industrial hydrogenation of vegetable and animal fattyacids. The total quantity in the oxidative agent composition (B) of atleast one linear saturated alkanol having 12 to 30 carbon atoms is about0.1 to about 10 wt %, preferably about 0.5 to about 7 wt %, andparticularly preferably about 3 to about 5 wt %, based in each case onthe total weight of the oxidative agent composition (B).

Further preferred oxidative coloring agents according to the presentinvention are characterized in that the composition (B) used accordingto the present invention contains:

about 1 to about 24 wt %, preferably about 4 to about 10 wt %,particularly preferably about 3 to about 6 wt % hydrogen peroxide(calculated as 100% H₂O₂), furthermore

at least one cosmetic oil in a total quantity from about 12 to about 70wt %, preferably about 14 to about 60 wt %, particularly preferablyabout 15 to about 52 wt %, and extraordinarily preferably about 17 toabout 35 wt %,

furthermore at least one surfactant in a total quantity from about 0.1to about 5 wt %, preferably about 0.5 to about 3 wt %, and particularlypreferably about 1 to about 2 wt %, as well as at least one linearsaturated alkanol having 12 to 30 carbon atoms, in a total quantity fromabout 0.1 to about 10 wt %, preferably about 0.5 to about 7 wt %, andparticularly preferably about 3 to about 5 wt %, where all “wt %”indications refer to the weight of composition (B).

The composition (A) used to manufacture the oxidative coloring agentsaccording to the present invention contains as obligatory ingredients atleast one oxidation dye precursor of the developer type and at least oneoxidation dye precursor of the coupler type.

Oxidation dye precursors can be divided in terms of their reactionbehavior into two categories: the so-called developer components andcoupler components.

Coupler components alone do not produce any significant color in thecontext of oxidative coloring, but instead always require the presenceof developer components. Developer components can form, with themselves,the actual dye.

The developer and coupler components are usually used in free form. Inthe case of substances having amino groups, however, it can be preferredto use them in salt form, in particular in the form of thehydrochlorides or hydrobromides or the sulfates.

It has been found, surprisingly, that hair coloring results withparticularly good washing fastness could be achieved using the oxidativecoloring agents according to the present invention. The reduction inhair damage was also surprisingly large.

Particularly preferred developer components are selected from at leastone compound of the group that is constituted from p-phenylenediamine,p-toluylenediamine, 2-(2-hydroxyethyl)-p-phenylenediamine,2-(1,2-dihydroxyethyl)-p-phenylenediamine,N,N-bis-(2-hydroxyethyl)-p-phenylenediamine,2-methoxymethyl-p-phenylenediamine,N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine,N,N-bis-(2-hydroxyethyl)-N,N′-bis-(4-aminophenyl)-1,3-diaminopropan-2-ol, bis-(2-hydroxy-5-aminophenyl)methane,1,3-bis-(2,5-diaminophenoxy)propan-2-ol,N,N-bis-(4-aminophenyl)-1,4-diazacycloheptane,1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane, p-aminophenol,4-amino-3-methylphenol, 4-amino-2-aminomethylphenol,4-amino-2-(1,2-dihydroxyethyl)phenol and4-amino-2-(diethylaminomethyl)phenol,4,5-diamino-1-(2-hydroxyethyl)pyrazole, 2,4,5,6-tetraaminopyrimidine,4-hydroxy-2,5,6-triaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine,the physiologically acceptable salts of these compounds, and mixtures ofthese developer components and developer component salts.

Very particularly preferred developer components are selected from4,5-diamino-1-(2-hydroxyethyl)pyrazole, p-toluylenediamine,2-(2-hydroxyethyl)-p-phenylenediamine,2-methoxymethyl-p-phenylenediamine,N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine, andmixtures of these compounds as well as physiologically acceptable saltsthereof. 4,5-Diamino-1-(2-hydroxyethyl)pyrazole and physiologicallyacceptable salts thereof are extraordinarily preferred.

The developer components are used preferably in a total quantity fromabout 0.01 to about 20 wt %, particularly preferably about 0.2 to about10 wt %, and extraordinarily preferably about 0.6 to about 5 wt %, basedin each case on the weight of composition (A).

The developer components are used preferably in a total quantity fromabout 0.005 to about 10 wt %, particularly preferably about 0.1 to about5 wt %, and extraordinarily preferably about 0.3 to about 2.5 wt %,based in each case on the weight of the ready-to-use coloring agent.

The term “ready-to-use coloring agent” is understood for purposes ofthis application as the mixture of all oxidation dye precursors and alloxidizing agents, optionally in combination with a suitable cosmeticcarrier, e.g. a cream base, as well as optionally in combination with atleast one substantive dye.

Coupler components for purposes of the invention allow at least onechemical residue of the coupler to be substituted with the oxidized formof the developer component, in which context a covalent bond formsbetween the coupler component and developer component. Couplers arepreferably cyclic compounds that carry on the cycle at least two groupsselected from (i) optionally substituted amino groups, and/or (ii)hydroxyl groups. If the cyclic compound is a six-membered ring(preferably aromatic), the aforesaid groups are then located preferablyin the ortho or meta position with respect to one another.

Preferred methods according to the present invention are characterizedin that the at least one oxidation dye precursor of the coupler type isselected from one of the following classes:

-   3-aminophenol (m-aminophenol) and/or derivatives thereof,-   3-aminoaniline (m-diaminobenzene) and/or derivatives thereof,-   2-aminoaniline (1,2-diaminobenzene; o-diaminobenzene) and/or    derivatives thereof,-   2-aminophenol (o-aminophenol) and/or derivatives thereof,-   naphthalene derivatives having at least one hydroxy group,-   di-resp. trihydroxybenzene and/or derivatives thereof,-   pyridine derivatives,-   pyrimidine derivatives,-   monohydroxyindole derivatives and/or monoaminoindole derivatives,-   monohydroxyindoline derivatives and/or monoaminoindoline derivatives-   pyrazolone derivatives such as e.g. 1-phenyl-3-methylpyrazol-5-one,-   morpholine derivatives such as e.g. 6-hydroxybenzomorpholine or    6-aminobenzomorpholine,-   quinoxaline derivatives such as e.g.    6-methyl-1,2,3,4-tetrahydroquinoxaline.

Mixtures of two or more compounds from one or more of these classes arelikewise preferred according to the present invention in the context ofthis embodiment.

Additional coupler components particularly preferred according to thepresent invention are selected from 3-aminophenol,5-amino-2-methylphenol, 3-amino-2-chloro-6-methylphenol,2-hydroxy-4-aminophenoxyethanol, 5-amino-4-chloro-2-methylphenol,5-(2-hydroxyethyl)amino-2-methylphenol, 2,4-dichloro-3-aminophenol,2-aminophenol, 3-phenylenediamine, 2-(2,4-diaminophenoxy)ethanol,1,3-bis-(2,4-diaminophenoxy)propane,1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene(=2-amino-4-hydroxyethylaminoanisole),1,3-bis-(2,4-diaminophenyl)propane,2,6-bis-(2′-hydroxyethylamino)-1-methylbenzene,2-({3-[(2-hydroxyethyl)amino]-4-methoxy-5-methylphenyl}amino)ethanol,2-({3-[(2-hydroxyethyl)amino]-2-methoxy-5-methylphenyl}amino)ethanol,2-({3-[(2-hydroxyethyl)amino]-4,5-dimethylphenyl}amino)ethanol2-[3-morpholin-4-ylphenyl)amino]ethanol,3-amino-4-(2-methoxyethoxy)-5-methylphenylamine,1-amino-3-bis-(2-hydroxyethyl)aminobenzene, resorcinol,2-methylresorcinol, 4-chlororesorcinol, 1,2,4-trihydroxybenzene,2-amino-3-hydroxypyridine, 3-amino-2-methylamino-6-methoxypyridine,2,6-dihydroxy-3,4-dimethylpyridine, 3,5-diamino-2,6-dimethoxypyridine,1-phenyl-3-methylpyrazol-5-one, 1-naphthol, 1,5-dihydroxynaphthalene,2,7-dihydroxynaphthalene, 1,7-dihydroxynaphthalene,1,8-dihydroxynapthalene, 4-hydroxyindole, 6-hydroxyindole,7-hydroxyindole, 4-hydroxyindoline, 6-hydroxyindoline,7-hydroxyindoline, or mixtures of these compounds, or thephysiologically acceptable salts of the aforesaid compounds.

Very particularly preferred in this context are 3-aminophenol,resorcinol, 2-methylresorcinol, 5-amino-2-methylphenol,2-(2,4-diaminophenoxy)ethanol, 1,3-bis-(2,4-diaminophenoxy)propane,1-methoxy-2-amino-4-(2′-hydroxyethylamino)benzene,2-amino-3-hydroxypyridine, and 1-naphthol, as well as physiologicallyacceptable salts thereof and mixtures of the components recited.

The at least one coupler component is used preferably in a totalquantity from about 0.01 to about 20 wt %, particularly preferably about0.2 to about 10 wt %, and extraordinarily preferably about 0.6 to about5 wt %, based in each case on the weight of composition (A).

The at least one coupler component is used preferably in a totalquantity from about 0.005 to about 10 wt %, preferably about 0.1 toabout 5 wt %, and extraordinarily preferably about 0.3 to about 2.5 wt%, based in each case on the weight of the oxidative coloring agentaccording to the present invention.

The following combinations of oxidation dye precursors of the developertype and of the coupler type are particularly preferred in the contextof the present invention, where the amine compounds and the nitrogenheterocycles can also be present in the form of their physiologicallyacceptable salts:

-   p-toluylenediamine/resorcinol;-   p-toluylenediamine/2-methylresorcinol;-   p-toluylenediamine/5-amino-2-methylphenol;-   p-toluylenediamine/3-aminophenol;-   p-toluylenediamine/2-(2,4-diaminophenoxy)ethanol;-   p-toluylenediamine/1,3-bis-(2,4-diaminophenoxy)propane;-   p-toluylenediamine/1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene;-   p-toluylenediamine/2-amino-3-hydroxypyridine;-   p-toluylenediamine/1-naphthol;-   2-(2-hydroxyethyl)-p-phenylenediamine/resorcinol;-   2-(2-hydroxyethyl)-p-phenylenediamine/2-methylresorcinol;-   2-(2-hydroxyethyl)-p-phenylenediamine/5-amino-2-methylphenol;-   2-(2-hydroxyethyl)-p-phenylenediamine/3-aminophenol;-   2-(2-hydroxyethyl)-p-phenylenediamine/2-(2,4-diaminophenoxy)ethanol;-   2-(2-hydroxyethyl)-p-phenylenediamine/1,3-bis-(2,4-diaminophenoxy)propane;-   2-(2-hydroxyethyl)-p-phenylenediamine    1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene;-   2-(2-hydroxyethyl)-p-phenylenediamine/2-amino-3-hydroxypyridine;-   2-(2-hydroxyethyl)-p-phenylenediamine/1-naphthol;-   2-methoxymethyl-p-phenylenediamine/resorcinol;-   2-methoxymethyl-p-phenylenediamine/2-methylresorcinol;-   2-methoxymethyl-p-phenylenediamine/5-amino-2-methylphenol;-   2-methoxymethyl-p-phenylenediamine/3-aminophenol;-   2-methoxymethyl-p-phenylenediamine/2-(2,4-diaminophenoxy)ethanol;-   2-methoxymethyl-p-phenylenediamine/1,3-bis-(2,4-diaminophenoxy)propane;-   2-methoxymethyl-p-phenylenediamine    1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene;-   2-methoxymethyl-p-phenylenediamine/2-amino-3-hydroxypyridine;-   2-methoxymethyl-p-phenylenediamine/1-naphthol;-   N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/resorcinol;-   N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/2-methylresorcinol;-   N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/5-amino-2-methylphenol;-   N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/3-aminophenol;-   N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine    2-(2,4-diaminophenoxy)ethanol;-   N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/1,3-bis-(2,4-diaminophenoxy)propane;-   N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene;-   N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/2-amino-3-hydroxypyridine;-   N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/1-naphthol;-   4,5-diamino-1-(2-hydroxyethyl)pyrazole/resorcinol;-   4,5-diamino-1-(2-hydroxyethyl)pyrazole/2-methylresorcinol;-   4,5-diamino-1-(2-hydroxyethyl)pyrazole/5-amino-2-methylphenol;-   4,5-diamino-1-(2-hydroxyethyl)pyrazole/3-aminophenol;-   4,5-diamino-1-(2-hydroxyethyl)pyrazole/2-(2,4-diaminophenoxy)ethanol;-   4,5-diamino-1-(2-hydroxyethyl)pyrazole/1,3-bis-(2,4-diaminophenoxy)propane;-   4,5-diamino-1-(2-hydroxyethyl)pyrazole    1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene;-   4,5-diamino-1-(2-hydroxyethyl)pyrazole/2-amino-3-hydroxypyridine;-   4,5-diamino-1-(2-hydroxyethyl)pyrazole/1-naphthol.

The combinations 4,5-diamino-1-(2-hydroxyethyl)pyrazole/3-aminophenoland p-toluylenediamine/3-aminophenol are particularly preferredaccording to the present invention. The combination4,5-diamino-1-(2-hydroxyethyl)pyrazole/3-aminophenol is extraordinarilypreferred, in particular in terms of improving washing fastness.

In order to achieve balanced and subtle toning, it is preferredaccording to the present invention if further color-imparting componentsare contained in the oxidative coloring agent according to the presentinvention.

In a further embodiment, the oxidative coloring agents according to thepresent invention can additionally contain at least one substantive dye.These are dyes that absorb directly onto the hair and do not require anoxidizing process for formation of the color. Substantive dyes areusually nitrophenylenediamines, nitroaminophenols, azo dyes,anthraquinones, or indophenols.

A further subject of the present application is a method for changingthe color of keratinic fibers, in particular human hair, thatencompasses the following method steps:

-   i) producing an oxidative coloring agent according to one of claims    1 to 14, for changing the color of keratinic fibers, immediately    before utilization by mixing at least one composition (A)    containing, in a cosmetically suitable carrier, at least one    alkalizing agent, at least one oxidation dye precursor of the    developer type, and at least one oxidation dye precursor of the    coupler type, with at least one composition (B) containing, in a    cosmetically suitable carrier, at least one cosmetic oil in a total    quantity from about 10 to about 80 wt % based on the weight of    composition (B), and hydrogen peroxide;-   ii) applying the ready-to-use oxidative coloring agent from method    step i) onto the keratinic fibers to be treated, and leaving the    oxidative coloring agent on the fibers for a contact time from about    5 to about 60 minutes;-   iii) rinsing out the fibers, the method being characterized in that    at least one of the compositions (A) or (B) contains at least one    4-morpholinomethyl-substituted silicone of formula (V),

in which

-   A denotes a structural unit (I), (II), or (III) bound via —O—

-   -   or an oligomeric or polymeric residue bound via —O— containing        structural units of formulas (I), (II), or (III), or half of an        oxygen atom connecting to a structural unit (III), or denotes        —OH,

-   * denotes a bond to one of the structural units (I), (II), or (III),    or denotes a terminal group B (Si-bound) or D (0-bound),

-   B denotes an —OH, —O—Si(CH₃)₃, —O—Si(CH₃)₂OH, —O—Si(CH₃)₂OCH₃ group,

-   D denotes an —H, —Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃ group,

-   a, b, and c denote integers from 0 to 990, with the provision that    a+b+c>0,

-   m, n, and o denote integers from 1 to 990.

A preferred method according to the present invention is characterizedin that the contact time in step ii) is about 15 to about 50 minutes,particularly preferably about 30 to about 45 minutes.

Regarding further preferred embodiments of the method according to thepresent invention recited above, the statements made about the preferredoxidative coloring agents apply mutatis mutandis.

The compositions (A) and (B) used to manufacture the oxidative coloringagents according to the present invention are preferably offered as amulti-component packaging unit (kit of parts).

Regarding further preferred embodiments of the kit of parts according tothe present invention recited above, the statements made about thepreferred oxidative coloring agents and the preferable methods applymutatis mutandis.

EXEMPLIFYING EMBODIMENTS Example 1

The color cream compositions (A)-1 (according to the present invention)and (A)-2 (not according to the present invention) presented in Table 1were mixed at a weight ratio of 1:1 either with the composition (B)-E(=oxidizing agent composition (B) having an oil content according to thepresent invention) presented in Table 2, or with the composition (B)—V(=oxidizing agent composition (B) having a lower oil content) presentedin Table 3, to yield a respective ready-to-use oxidative coloring agent.The ready-to-use oxidative coloring agent was then applied onto the testskeins, specifically at a rate of 4 g coloring agent per gram of hair.

The oxidative coloring agent remained on the skeins for 30 minutes ineach case. The skeins were then rinsed out for 2 minutes using warm (32°C.) tap water at a flow rate of 0.5 liter per minute. The skeins werethen combed three times before the actual combability measurements (10comb strokes each on 20 skeins) were carried out.

TABLE 1 Compositions (A): color creams (quantities indicated in wt %)(A)-1 According to the (A)-2 present invention Comparison Belsil ADM8301 E* 2.0 — Toluene-2,5-Diamine Sulfate 0.02 0.022-Amino-4-Hydroxyethylaminoanisole 0.02 0.02 Sulfate(1-methoxy-2-amino-4-(2′- hydroxyethylamino)benzene sulfate)4-Amino-2-Hydroxytoluene 0.01 0.01 Cetearyl Alcohol 14 14 GlycerylStearate 1.4 1.4 Ammonium Hydroxide 6.8 6.8 Ceteareth-20 3.5 3.5Octyldodecanol 1.0 1.0 Sodium Laureth Sulfate 0.5 0.5 1,3-Butyleneglycol 3.5 3.5 Sodium Cetearyl Sulfate 1.0 1.0 Oleic Acid 0.1 0.1Perfume (Fragrance) 0.5 0.5 Potassium Stearate 0.5 0.5 Sodium Sulfite0.2 0.2 Tetrasodium EDTA 0.3 0.3 Carbomer 0.3 0.3 Polyquaternium-39 (exMerquat 3330) 0.05 0.05 Potassium Hydroxide 0.08 0.08 Ascorbic Acid 0.020.02 Linoleamidopropyl PG-Dimonium 0.1 0.1 Chloride Phosphate SodiumSulfate 0.1 0.1 Citric Acid 0.002 0.002 CI 77891 (Titanium Dioxide) 0.30.3 Aqua (Water, Eau) to 100 to 100 *Belsil ADM 8301 E (ex WackerSilicones) = microemulsion; constituents (INCI:Amodimethicone/Morpholinomethyl Silsesquioxane (10 wt %); Trideceth-5 (5wt %); glycerol (2.5 wt %); phenoxyethanol (0.45 wt %), remainder: water(82.05 wt %))

TABLE 2 Oxidizing agent composition (B)-E having oil content accordingto the present invention (quantities indicated in wt %) ParaffinumLiquidum 17.00 Cetearyl Alcohol 4.00 Dipicolinic acid 0.10 DisodiumPyrophosphate 0.10 Potassium Hydroxide 0.12 Etidronic Acid 0.20 PEG-40Castor Oil 0.70 Sodium Cetearyl Sulfate 0.40 H₂O₂ (active content) 6.00Water to 100.0

TABLE 3 Oxidizing agent composition (B)-V having oil content notaccording to the present invention (quantities indicated in wt %)Paraffinum Liquidum 0.5 Cetearyl Alcohol 4.0 Dipicolinic acid 0.1Disodium Pyrophosphate 0.1 Potassium hydroxide 0.1 1,2-Propylene glycol1.0 1-Hydroxyethane-1,1-Diphosphonic Acid (Etidronic Acid) 0.1Steartrimonium Chloride 0.5 Ceteareth-20 1.0 H₂O₂ (active content) 12.0Water to 100

TABLE 4 Wet combability; combing work (mJ) Combing Relative work change(mJ) (%) (A)-2 + (B)-V (comparison) 1250 100 (A)-2 + (B)-E (comparison)905 72 (A)-1 + (B)-V (comparison) 980 78 (A)-1 + (B)-E (according to thepresent invention) 728 58

TABLE 5 Split count after 20,000 comb strokes (proportion as %) Splitcount Relative (%) change (%) (A)-2 + (B)-V (comparison) 1.5 100 (A)-2 +(B)-E (comparison) 1.3 87 (A)-1 + (B)-V (comparison) 1.1 73 (A)-1 +(B)-E (according to the present 0.9 60 invention)

As shown by the data presented in Tables 4 and 5, both the content of4-morpholinomethyl-substituted silicone of formula (V) alone (containedin the raw material Belsil ADM 8301 E), and the use of an oxidizingagent composition (B) having a high oil content ((B)-E) alone, alreadyhave a positive effect on protection of the hair from oxidative damage:not only is combing work reduced by 22 resp. 28% (lower combing workbeing equivalent to less hair damage), but the number of splits causedby standardized test combing is reduced by 27 resp. 13%.

In contrast, the oxidative coloring agent according to the presentinvention, which combines 4-morpholinomethyl-substituted silicones offormula (V) with an oxidizing agent composition (B) having a high oilcontent, brings a further very appreciable reduction in wet combing workand the splitting rate.

What is claimed is:
 1. An oxidative coloring agent for oxidativelychanging a color of keratinic fibers, wherein the oxidative coloringagent is produced immediately before utilization by mixing at least onecomposition (A) containing, in a cosmetically suitable carrier, at leastone alkalizing agent, at least one oxidation dye precursor of thedeveloper type, and at least one oxidation dye precursor of the couplertype, with at least one composition (B) containing, in a cosmeticallysuitable carrier, at least one cosmetic oil in a total quantity fromabout 10 to about 80 wt % based on a weight of composition (B), andhydrogen peroxide, wherein at least one of the compositions (A) or (B)contains at least one 4-morpholinomethyl-substituted silicone of formula(V),

in which A denotes a structural unit (I), (II), or (III) bound via —O—

or an oligomeric or polymeric residue bound via —O— containingstructural units of formulas (I), (II), or (III), or half of an oxygenatom connecting to a structural unit (III), or denotes —OH, * denotes abond to one of the structural units (I), (II), or (III), or denotes aterminal group B (Si-bound) or D (O-bound), B denotes an —OH,—O—Si(CH₃)₃, —O—Si(CH₃)₂OH, —O—Si(CH₃)₂OCH₃ group, D denotes an —H,—Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃ group, a, b, and c denote integersfrom 0 to 990, with the provision that a+b+c>0, m, n, and o denoteintegers from 1 to
 990. 2. The oxidative coloring agent according toclaim 1, wherein the keratinic fibers are human hair.
 3. The oxidativecoloring agent according to claim 1, wherein composition (A),composition (B), or both contains at least one4-morpholinomethyl-substituted silicone of formula (V) in whichm>(n+o)resp.(a+b+c)>(n+o).
 4. The oxidative coloring agent according toclaim 1, wherein the oxidative coloring agent contains at least one4-morpholinomethyl-substituted silicone in a total quantity from about0.001 to about 5 wt %, based in each case on the total weight of theoxidative coloring agent.
 5. The oxidative coloring agent according toclaim 1, wherein the oxidative coloring agent contains at least one4-morpholinomethyl-substituted silicone of formula (V) that respectivelycomprises at least one of the structural units of formulas (I), (II),and (III), in a total quantity from about 0.001 to about 5 wt %, basedin each case on the total weight of the oxidative coloring agent.
 6. Theoxidative coloring agent according to claim 1, wherein the oxidativecoloring agent contains a hydroxy-terminated4-morpholinomethyl-substituted silicone in which a molar ratio ofhydroxy to alkoxy is in the range from about 0.2:1 to about 0.4:1. 7.The oxidative coloring agent according to claim 1, wherein aweight-average molar mass of the 4-morpholinomethyl-substituted siliconeof formula (V) is in the range from about 2,000 to about 1,000,000gmol⁻¹.
 8. The oxidative coloring agent according to claim 1, whereinthe 4-morpholinomethyl-substituted silicone of formula (V) is present ina form of an oil-in-water emulsion in which a number-average size ofsilicone particles in the oil-in-water emulsion is in the range fromabout 3 to about 500 nm.
 9. The oxidative coloring agent according toclaim 1, wherein the at least one cosmetic oil that is contained incomposition (B) in a total quantity from about 10 to about 80 wt %,based on the weight of composition (B), is chosen from natural andsynthetic hydrocarbons.
 10. The oxidative coloring agent according toclaim 9, wherein the at least one cosmetic oil is chosen from paraffinoils and C₁₈ to C₃₀ isoparaffins.
 11. The oxidative coloring agentaccording to claim 10, wherein the at least one cosmetic oil is chosenfrom isoeicosane, polyisobutenes, and polydecenes, C₈ to C₁₆isoparaffins, and 1,3-di-(2-ethylhexyl)cyclohexane; benzoic acid estersof linear or branched C₈₋₂₂ alkanols; fatty alcohols having 6 to 30carbon atoms, which are unsaturated or branched and saturated orbranched and unsaturated; triglycerides of linear or branched, saturatedor unsaturated, optionally hydroxylated C₈₋₃₀ fatty acids; dicarboxylicacid esters of linear or branched C₂ to C₁₀ alkanols; esters of linearor branched, saturated or unsaturated fatty alcohols having 2 to 30carbon atoms with linear or branched, saturated or unsaturated fattyacids having 2 to 30 carbon atoms, which can be hydroxylated; additionproducts of 1 to 5 propylene oxide units with mono- or polyvalent C₈₋₂₂alkanols; addition products of at least 6 ethylene oxide and/orpropylene oxide units with mono- or polyvalent C₃₋₂₂ alkanols; C₈ to C₂₂fatty alcohol esters of monovalent or polyvalent C₂ to C₇hydroxycarboxylic acids; symmetrical, asymmetrical, or cyclic esters ofcarbonic acid with C₃₋₂₂ alkanols, C₃₋₂₂ alkanediols, or C₃₋₂₂alkanetriols; esters of dimers of unsaturated C₁₂ to C₂₂ fatty acids(dimer fatty acids) with monovalent linear, branched, or cyclic C₂ toC₁₈ alkanols or with polyvalent linear or branched C₂ to C₆ alkanols;silicone oils; and mixtures of the aforementioned substances.
 12. Theoxidative coloring agent according to claim 1, wherein composition (B)contains the at least one cosmetic oil in a total quantity from about 12to about 70 wt %.
 13. The oxidative coloring agent according to claim 1,wherein composition (B) contains: about 1 to about 24 wt % hydrogenperoxide (calculated as 100% H₂O₂), the at least one cosmetic oil in atotal quantity from about 12 to about 70 wt %, at least one surfactantin a total quantity from about 0.1 to about 5 wt %, and at least onelinear saturated alkanol having 12 to 30 carbon atoms, in a totalquantity from about 0.1 to about 10 wt %, where all “wt %” indicationsrefer to the weight of composition (B).
 14. The oxidative coloring agentaccording to claim 1, wherein the oxidative coloring agent contains theat least one cosmetic oil in a total quantity from about 5 to about 50wt %, based in each case on the total weight of the oxidative coloringagent.
 15. The oxidative coloring agent according to claim 1, whereinthe at least one 4-morpholinomethyl-substituted silicone of formula (V)is contained in composition (A).
 16. The oxidative coloring agentaccording to claim 1, wherein the at least one4-morpholinomethyl-substituted silicone of formula (V) is contained incomposition (B).
 17. The oxidative coloring agent according to claim 1,wherein a combination of the at least one oxidation dye precursor of thedeveloper type and the at least one oxidation dye precursor of thecoupler type is selected from at least one of the followingcombinations, where the amine compounds and the nitrogen heterocyclescan also be present in a form of their physiologically acceptable salts:p-toluylenediamine/resorcinol; p-toluylenediamine/2-methylresorcinol;p-toluylenediamine/5-amino-2-methylphenol;p-toluylenediamine/3-aminophenol;p-toluylenediamine/2-(2,4-diaminophenoxy)ethanol;p-toluylenediamine/1,3-bis-(2,4-diaminophenoxy)propane;p-toluylenediamine/1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene;p-toluylenediamine/2-amino-3-hydroxypyridine;p-toluylenediamine/1-naphthol;2-(2-hydroxyethyl)-p-phenylenediamine/resorcinol;2-(2-hydroxyethyl)-p-phenylenediamine/2-methylresorcinol;2-(2-hydroxyethyl)-p-phenylenediamine/5-amino-2-methylphenol;2-(2-hydroxyethyl)-p-phenylenediamine/3-aminophenol;2-(2-hydroxyethyl)-p-phenylenediamine/2-(2,4-diaminophenoxy)ethanol;2-(2-hydroxyethyl)-p-phenylenediamine/1,3-bis-(2,4-diaminophenoxy)propane;2-(2-hydroxyethyl)-p-phenylenediamine1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene;2-(2-hydroxyethyl)-p-phenylenediamine/2-amino-3-hydroxypyridine;2-(2-hydroxyethyl)-p-phenylenediamine/1-naphthol;2-methoxymethyl-p-phenylenediamine/resorcinol;2-methoxymethyl-p-phenylenediamine/2-methylresorcinol;2-methoxymethyl-p-phenylenediamine/5-amino-2-methylphenol;2-methoxymethyl-p-phenylenediamine/3-aminophenol;2-methoxymethyl-p-phenylenediamine/2-(2,4-diaminophenoxy)ethanol;2-methoxymethyl-p-phenylenediamine/1,3-bis-(2,4-diaminophenoxy)propane;2-methoxymethyl-p-phenylenediamine1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene;2-methoxymethyl-p-phenylenediamine/2-amino-3-hydroxypyridine;2-methoxymethyl-p-phenylenediamine/1-naphthol;N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/resorcinol;N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine2-methylresorcinol;N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/5-amino-2-methylphenol;N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine3-aminophenol;N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/2-(2,4-diaminophenoxy)ethanol;N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/1,3-bis-(2,4-diaminophenoxy)propane;N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene;N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/2-amino-3-hydroxypyridine;N-(4-amino-3-methylphenyl)-N-[3-(1H-imidazol-1-yl)propyl]amine/1-naphthol;4,5-diamino-1-(2-hydroxyethyl)pyrazole/resorcinol;4,5-diamino-1-(2-hydroxyethyl)pyrazole/2-methylresorcinol;4,5-diamino-1-(2-hydroxyethyl)pyrazole/5-amino-2-methylphenol;4,5-diamino-1-(2-hydroxyethyl)pyrazole/3-aminophenol;4,5-diamino-1-(2-hydroxyethyl)pyrazole/2-(2,4-diaminophenoxy)ethanol;4,5-diamino-1-(2-hydroxyethyl)pyrazole/1,3-bis-(2,4-diaminophenoxy)propane;4,5-diamino-1-(2-hydroxyethyl)pyrazole1-methoxy-2-amino-4-(2-hydroxyethylamino)benzene;4,5-diamino-1-(2-hydroxyethyl)pyrazole/2-amino-3-hydroxypyridine; and4,5-diamino-1-(2-hydroxyethyl)pyrazole/1-naphthol.
 18. A method forchanging a color of keratinic fibers, the method comprising the stepsof: i) producing an oxidative coloring agent for changing the color ofkeratinic fibers immediately before utilization by mixing at least onecomposition (A) comprising, in a cosmetically suitable carrier, at leastone alkalizing agent, at least one oxidation dye precursor of thedeveloper type, and at least one oxidation dye precursor of the couplertype, with at least one composition (B) containing, in a cosmeticallysuitable carrier, at least one cosmetic oil in a total quantity fromabout 10 to about 80 wt % based on a weight of composition (B), andhydrogen peroxide; ii) applying the oxidative coloring agent from methodstep i) onto the keratinic fibers to be treated, and leaving theoxidative coloring agent on the keratinic fibers for a contact time fromabout 5 to about 60 minutes; and iii) rinsing out the keratinic fibers,wherein at least one of the compositions (A) or (B) contains at leastone 4-morpholinomethyl-substituted silicone of formula (V),

in which A denotes a structural unit (I), (II), or (III) bound via —O—

or an oligomeric or polymeric residue bound via —O— containingstructural units of formulas (I), (II), or (III), or half of an oxygenatom connecting to a structural unit (III), or denotes —OH, * denotes abond to one of the structural units (I), (II), or (III), or denotes aterminal group B (Si-bound) or D (O-bound), B denotes an —OH,—O—Si(CH₃)₃, —O—Si(CH₃)₂O—Si(CH₃)₂OCH₃ group, D denotes an —H,—Si(CH₃)₃, —Si(CH₃)₂OH, —Si(CH₃)₂OCH₃ group, a, b, and c denote integersfrom 0 to 990, with the provision that a+b+c>0, m, n, and o denoteintegers from 1 to
 990. 19. The method for changing the color ofkeratinic fibers according to claim 18, wherein the method is forchanging a color of human hair.